U.S. patent application number 17/407146 was filed with the patent office on 2021-12-09 for luminescent particle and compound.
This patent application is currently assigned to FUJIFILM Corporation. The applicant listed for this patent is FUJIFILM Corporation. Invention is credited to Naoyuki HANAKI, Yoshinori KANAZAWA, Kazuhei KANEKO, Kouitsu SASAKI, Kousuke WATANABE, Tomoaki YOSHIOKA.
Application Number | 20210380881 17/407146 |
Document ID | / |
Family ID | 1000005787272 |
Filed Date | 2021-12-09 |
United States Patent
Application |
20210380881 |
Kind Code |
A1 |
WATANABE; Kousuke ; et
al. |
December 9, 2021 |
LUMINESCENT PARTICLE AND COMPOUND
Abstract
An object of the present invention is to provide a luminescent
particle having an emission maximum wavelength in a long wavelength
range of 680 nm or longer and exhibiting a high quantum yield; and
a compound having an emission maximum wavelength in a long
wavelength range of 680 nm or longer and exhibiting a high quantum
yield in the particles. According to the present invention,
provided is a luminescent particle containing at least one kind of
compound represented by Formula (1) (definitions of substituents in
the formula are as set forth in the description) and a particle.
##STR00001##
Inventors: |
WATANABE; Kousuke;
(Kanagawa, JP) ; HANAKI; Naoyuki; (Kanagawa,
JP) ; SASAKI; Kouitsu; (Kanagawa, JP) ;
YOSHIOKA; Tomoaki; (Kanagawa, JP) ; KANEKO;
Kazuhei; (Kanagawa, JP) ; KANAZAWA; Yoshinori;
(Kanagawa, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
FUJIFILM Corporation
Tokyo
JP
|
Family ID: |
1000005787272 |
Appl. No.: |
17/407146 |
Filed: |
August 19, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16282327 |
Feb 22, 2019 |
11136500 |
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17407146 |
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PCT/JP2017/030054 |
Aug 23, 2017 |
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16282327 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 11/06 20130101;
C09K 11/0827 20130101; C09B 23/00 20130101; C09K 11/02 20130101;
C09K 2211/1044 20130101; C07F 5/022 20130101; C09K 11/665 20130101;
C07F 5/02 20130101; C09K 2211/188 20130101 |
International
Class: |
C09K 11/66 20060101
C09K011/66; C07F 5/02 20060101 C07F005/02; C09B 23/00 20060101
C09B023/00; C09K 11/06 20060101 C09K011/06; C09K 11/02 20060101
C09K011/02; C09K 11/08 20060101 C09K011/08 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 23, 2016 |
JP |
2016-162613 |
Mar 10, 2017 |
JP |
2017-046742 |
Jul 26, 2017 |
JP |
2017-144722 |
Claims
1. A compound represented by Formula (3): ##STR00076## in the
formula, R.sup.11 and R.sup.15 each independently represent an aryl
group which may have a substituent; R.sup.12 and R.sup.14 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent; X.sup.1 and X.sup.2 each
independently represent a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, a hydroxy group, an alkoxy group, an
aryloxy group, an alkylthio group, an arylthio group, an ethenyl
group, or an ethynyl group, each of which may have a substituent,
and X.sup.1 and X.sup.2 may be bonded to each other to form a ring;
Ar.sup.1 and Ar.sup.2 each independently represent an aryl group or
a heterocyclic group, each of which may have a substituent;
R.sup.31, R.sup.32, R.sup.34 and R.sup.35 each represent a fluorine
atom, and R.sup.33 represents a hydrogen atom or a fluorine atom;
and L.sup.1 and L.sup.2 each represent Formula (L-1):
##STR00077##
2. A compound represented by Formula (6): ##STR00078## in the
formula, R.sup.11 and R.sup.15 each independently represent an aryl
group which may have a substituent; R.sup.12 and R.sup.14 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent; X.sup.1 and X.sup.2 each
independently represent a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, a hydroxy group, an alkoxy group, an
aryloxy group, an alkylthio group, an arylthio group, an ethenyl
group, or an ethynyl group, each of which may have a substituent,
and X.sup.1 and X.sup.2 may be bonded to each other to form a ring;
R.sup.31 to R.sup.35 each independently represent a hydrogen atom,
a halogen atom, an alkyl group, an aryl group, a heterocyclic
group, an ethenyl group, an ethynyl group, an amino group, an acyl
group, a cyano group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent, and any one of R.sup.31, R.sup.32, R.sup.33, R.sup.34
or R.sup.35 is a hydrogen atom; R.sup.51 and R.sup.52 each
independently represent an alkyl group, an aryl group, a heteroaryl
group, an amino group, an acyl group, an alkoxy group, an aryloxy
group, an alkylthio group, or an arylthio group, each of which may
have a substituent; Q.sup.1 and Q.sup.2 each independently
represent an aromatic hydrocarbon ring or an aromatic heterocyclic
ring, each of which may have a substituent; and L.sup.1 and L.sup.2
each represent Formula (L-1): ##STR00079##
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of and claims
the priority benefits of U.S. application Ser. No. 16/282,327,
filed on Feb. 22, 2019, now allowed, which is a Continuation of PCT
International Application No. PCT/JP2017/030054 filed on Aug. 23,
2017, which claims priority under 35 U.S.0 .sctn.119(a) to Japanese
Patent Application No. 2016-162613 filed on Aug. 23, 2016, Japanese
Patent Application No. 2017-046742 filed on Mar. 10, 2017 and
Japanese Patent Application No. 2017-144722 filed on Jul. 26, 2017.
Each of the above applications is hereby expressly incorporated by
reference, in its entirety, into the present application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The present invention relates to a luminescent particle
containing a compound having a specific structure and a novel
compound useful as a dye.
2. Description of the Related Art
[0003] A fluorescence detection method is widely used as a highly
sensitive and easy measurement method for quantifying a protein, an
enzyme, an inorganic compound, or the like. The fluorescence
detection method is a method of confirming the presence of a
substance to be measured by detecting the fluorescence emitted in
the case where excitation light of a specific wavelength is
irradiated to a sample considered to contain a substance to be
measured which is excited by the light of a specific wavelength to
emit fluorescence. In the case where the substance to be measured
is not a fluorescent substance, for example, the presence of the
substance to be measured can be confirmed by bring a substance in
which a substance specifically binding to the substance to be
measured is labeled with a fluorescent dye into contact with a
sample, and then detecting the fluorescence emitted in the case
where excitation light is irradiated in the same manner as
described above.
[0004] JP3442777B discloses fluorescent microparticles produced by
blending an initial donor dye having a preferable excitation peak
and a final receptor dye having a preferable luminescence peak in
polymer microparticles. In JP3442777B, it is described that a
polyazaindacene dye is used as the dye.
[0005] Olivier Galangau et al., Org. Biomol. Chem., 2010, Vol. 8,
pp. 4546 to 4553 discloses that a novel distyryl BODIPY.sup.R
(registered trademark, abbreviation of boron-dipyrromethene) dye is
designed and synthesized, and the synthesized distyryl BODIPY.sup.R
dye has been analyzed for absorption and emission spectra in a
chloromethane solution.
SUMMARY OF THE INVENTION
[0006] The fluorescent microparticles described in JP3442777B have
a preferable effective Stokes shift, but have a problem of low
quantum yield. In Olivier Galangau et al., Org. Biomol. Chem.,
2010, Vol. 8, pp. 4546 to 4553, absorption and emission spectra of
a dye solution are analyzed, but there is no description about
incorporation of a dye into particles.
[0007] An object of the present invention is to provide a
luminescent particle having an emission maximum wavelength in a
long wavelength range of 680 nm or longer and exhibiting a high
quantum yield; and a compound having an emission maximum wavelength
in a long wavelength range of 680 nm or longer and exhibiting a
high quantum yield in the particles.
[0008] As a result of extensive studies to achieve the foregoing
object, the present inventors have found that a luminescent
particle having an emission maximum wavelength in a long wavelength
range of 680 nm or longer and exhibiting a high quantum yield can
be produced by producing a luminescent particle using a novel
compound having a specific structure. The present invention has
been completed based on these findings.
[0009] That is, according to the present invention, the following
inventions are provided.
[0010] [1] A luminescent particle containing at least one kind of
compound represented by Formula (1) and a particle:
##STR00002##
[0011] in the formula, R.sup.11 to R.sup.15 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent, and at least three of R.sup.11 to R.sup.15 represent
atoms or groups other than hydrogen atoms; X.sup.1 and X.sup.2 each
independently represent a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, a hydroxy group, an alkoxy group, an
aryloxy group, an alkylthio group, an arylthio group, an ethenyl
group, or an ethynyl group, each of which may have a substituent,
and X.sup.1 and X.sup.2 may be bonded to each other to form a ring;
Ar.sup.1 and Ar.sup.2 each independently represent an aryl group or
a heterocyclic group, each of which may have a substituent; and
L.sup.I and L.sup.2 each independently represent any one of Formula
(L-1), Formula (L-2), Formula (L-3) or Formula (L-4);
##STR00003##
[0012] in the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent; and A represents --O--, --S--, or --NH--.
[0013] [2] The luminescent particle according to [1], in which the
particle is a latex particle.
[0014] [3] The luminescent particle according to [1] or [2], in
which the particle has a carboxyl group.
[0015] [4] The luminescent particle according to any one of [1] to
[3], which has an average particle diameter of 30 to 500 nm.
[0016] [5] The luminescent particle according to any one of [1] to
[4], in which the compound represented by Formula (1) is a compound
represented by Formula (2):
##STR00004##
[0017] in the formula, R.sup.11 to R.sup.15 , X.sup.1, X.sup.2,
Ar.sup.1, and Ar.sup.2 are as defined in Formula (1), and L.sup.21
and L.sup.22 each independently represent a group represented by
Formula (L-1) or Formula (L-2):
##STR00005##
[0018] [6] The luminescent particle according to any one of [1] to
[4], in which the compound represented by Formula (1) is a compound
represented by Formula (3):
##STR00006##
[0019] in the formula, R.sup.11, R.sup.12, R.sup.14, R.sup.15,
A.sup.r1, A.sup.r2, L.sup.1 , and L.sup.2 are as defined in Formula
(1), provided that at least two of R.sup.11, R.sup.12, R.sup.14,
and R.sup.15 are atoms or groups other than hydrogen atoms;
R.sup.31 to R.sup.35 each independently represent a hydrogen atom,
a halogen atom, an alkyl group, an aryl group, a heterocyclic
group, an ethenyl group, an ethynyl group, an amino group, an acyl
group, a cyano group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent; and any one of R.sup.31, R.sup.32, R.sup.34 or
R.sup.35 is a group consisting of two or more atoms.
[0020] [7] The luminescent particle according to any one of [1] to
[4], in which the compound represented by Formula (1) is a compound
represented by Formula (4):
##STR00007##
[0021] in the formula, R.sup.12, R.sup.13, R.sup.14, X.sup.1,
X.sup.2, Ar.sup.1, Ar.sup.2, L.sup.1, and L.sup.2 are as defined in
Formula (I), provided that at least one of R.sup.12, R.sup.13,
R.sup.14 is an atom or group other than a hydrogen atom; and
R.sup.41 and R.sup.42 each independently represent an aryl group, a
heterocyclic group, an ethenyl group, or an ethynyl group, each of
which may have a substituent.
[0022] [8] The luminescent particle according to any one of [1] to
[5] and [7], in which the compound represented by Formula (4) is a
compound represented by Formula (7):
##STR00008##
[0023] in the formula, R.sup.12, R.sup.13, R.sup.14, R.sup.41,
R.sup.42, X.sup.1, X.sup.2, Ar.sup.1, and Ar.sup.2 are as defined
in Formula (4), provided that at least one of R.sup.12, R.sup.13 or
R.sup.14 is an atom or group other than a hydrogen atom; and
L.sup.23 and L.sup.24 each independently represent a group
represented by Formula (L-1) or (L-2).
##STR00009##
[0024] [9] The luminescent particle according to any one of [1] to
[5], [7] and [8], in which the compound represented by Formula (7)
is a compound represented by Formula (8):
##STR00010##
[0025] in the formula, R.sup.12, R.sup.14, R.sup.41, R.sup.42,
X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2, L.sup.23, and L.sup.24 are as
defined in Formula (7); R.sup.31 to R.sup.35 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, a cyano group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent; and any one of R.sup.31, R.sup.32,
R.sup.33, R.sup.34 or R.sup.35 is a hydrogen atom.
[0026] [10] The luminescent particle according to any one of [1] to
[5] and [7] to [9], in which the compound represented by Formula
(8) is a compound represented by Formula (9):
##STR00011##
[0027] in the formula, R.sup.12, R.sup.14, R.sup.41, R.sup.42,
R.sup.31 to R.sup.35, X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2,
L.sup.23, and L.sup.24 are as defined in Formula (8); R.sup.61 and
R.sup.62 each independently represent an alkyl group, an alkenyl
group, an aryl group, a heteroaryl group, an amino group, an acyl
group, an alkoxy group, an aryloxy group, an alkylthio group, or an
arylthio group, each of which may have a substituent; Q.sup.1 and
Q.sup.2 each independently represent an aromatic hydrocarbon ring
or an aromatic heterocyclic ring, each of which may have a
substituent; and R.sup.61 and Q.sup.1, and R.sup.62 and Q.sup.2
each may form a fused ring structure.
[0028] [11] The luminescent particle according to any one of [1] to
[4], in which the compound represented by Formula (1) is a compound
represented by Formula (5):
##STR00012##
[0029] in the formula, R.sup.11 to R.sup.15, X.sup.1, X.sup.2,
L.sup.1, and L.sup.2 are as defined in Formula (1); R.sup.51 and
R.sup.52 each independently represent an alkyl group, an aryl
group, a heteroaryl group, an amino group, an acyl group, an alkoxy
group, an aryloxy group, an alkylthio group, or an arylthio group,
each of which may have a substituent; and Q.sup.1 and Q.sup.2 each
independently represent an aromatic hydrocarbon ring or an aromatic
heterocyclic ring, each of which may have a substituent.
[0030] [12] The luminescent particle according to any one of [1] to
[4] and [11], in which the compound represented by Formula (5) is a
compound represented by Formula (6):
##STR00013##
[0031] in the formula, R.sup.11, R.sup.12, R.sup.14, R.sup.15,
X.sup.1, X.sup.2, L.sup.1, and L.sup.2 are as defined in Formula
(5); R.sup.31 to R.sup.35 each independently represent a hydrogen
atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic
group, an ethenyl group, an ethynyl group, an amino group, an acyl
group, a cyano group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent, and any one of R.sup.31, R.sup.32, R.sup.33, R.sup.34
or R.sup.35 is a hydrogen atom;
[0032] R.sup.51 and R.sup.52 each independently represent an alkyl
group, an aryl group, a heteroaryl group, an amino group, an acyl
group, an alkoxy group, an aryloxy group, an alkylthio group, or an
arylthio group, each of which may have a substituent; and Q.sup.1
and Q.sup.2 each independently represent an aromatic hydrocarbon
ring or an aromatic heterocyclic ring, each of which may have a
substituent.
[0033] [13] The luminescent particle according to any one of [1] to
[12], in which the maximum emission wavelength is 650 nm or
longer.
[0034] [14] A compound represented by Formula (3):
##STR00014##
[0035] in the formula, R.sup.11, R.sup.12, R.sup.4, and R.sup.15
each independently represent a hydrogen atom, a halogen atom, an
alkyl group, an aryl group, a heterocyclic group, an ethenyl group,
an ethynyl group, an amino group, an acyl group, an alkoxy group,
an aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and at least two of R.sup.11,
R.sup.12, R.sup.14, and R.sup.15 are atoms or groups other than
hydrogen atoms; X.sup.1 and X.sup.2 each independently represent a
halogen atom, an alkyl group, an aryl group, a heterocyclic group,
a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio
group, an arylthio group, an ethenyl group, or an ethynyl group,
each of which may have a substituent, and X.sup.1 and X.sup.2 may
be bonded to each other to form a ring; Ar.sup.1 and Ar.sup.2 each
independently represent an aryl group or a heterocyclic group, each
of which may have a substituent; R.sup.31 to R.sup.35 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, a cyano group, an
alkoxy group, an aryloxy group, an alkylthio group, or an arylthio
group, each of which may have a substituent, and any one of
R.sup.31, R.sup.32, R.sup.34 or R.sup.35 is a group consisting of
two or more atoms; and L.sup.1 and L.sup.2 each independently
represent any one of Formula (L-1), Formula (L-2), Formula (L-3) or
Formula (L-4);
##STR00015##
[0036] in the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent; and A represents --O--, --S--, or --NH--.
[0037] [15] A compound represented by Formula (4):
##STR00016##
[0038] in the formula, R.sup.12, R.sup.13, and R.sup.14 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and at least one of R.sup.12,
R.sup.13 or R.sup.14 is an atom or group other than a hydrogen
atom; X.sup.1 and X.sup.2 each independently represent a halogen
atom, an alkyl group, an aryl group, a heterocyclic group, a
hydroxy group, an alkoxy group, an aryloxy group, an alkylthio
group, an arylthio group, an ethenyl group, or an ethynyl group,
each of which may have a substituent, and X.sup.1 and X.sup.2 may
be bonded to each other to form a ring; Ar.sup.1 and Ar.sup.2 each
independently represent an aryl group or a heterocyclic group, each
of which may have a substituent; R.sup.41 and R.sup.42 each
independently represent an aryl group, a heterocyclic group, an
ethenyl group, or an ethynyl group, each of which may have a
substituent; and L.sup.1 and L.sup.2 each independently represent
any one of Formula (L-1), (L-2), (L-3) or (L-4);
##STR00017##
[0039] in the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent; and A represents --O--, --S--, or --NH--.
[0040] [16] The compound according to [15], which is represented by
Formula (7):
##STR00018##
[0041] in the formula, R.sup.12, R.sup.13, R.sup.14, R.sup.41,
R.sup.42, X.sup.1, X.sup.2, Ar.sup.1, and Ar.sup.2 are as defined
in Formula (4), provided that at least one of R.sup.12, R.sup.13 or
R.sup.14 is an atom or group other than a hydrogen atom; and
L.sup.23 and L.sup.24 each independently represent a group
represented by Formula (L-1) or Formula (L-2).
##STR00019##
[0042] [17] The compound according to [15] or [16], which is
represented by Formula (8):
##STR00020##
[0043] in the formula, R.sup.12, R.sup.14, R.sup.41, R.sup.42,
X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2, L.sup.23, and L.sup.24 are as
defined in Formula (7); and R.sup.31 to R.sup.35 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, a cyano group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and any one of R.sup.31, R.sup.32,
R.sup.33, R.sup.34 or R.sup.35 is a hydrogen atom.
[0044] [18] The compound according to any one of [15] to [17],
which is represented by Formula (9):
##STR00021##
[0045] in the formula, R.sup.12, R.sup.14, R.sup.41, R.sup.42,
R.sup.31 to R.sup.35, X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2,
L.sup.23, and L.sup.24 are as defined in Formula (8); R.sup.61 and
R.sup.62 each independently represent an alkyl group, an alkenyl
group, an aryl group, a heteroaiyl group, an amino group, an acyl
group, an alkoxy group, an aryloxy group, an alkylthio group, or an
arylthio group, each of which may have a substituent; Q.sup.1 and
Q.sup.2 each independently represent an aromatic hydrocarbon ring
or an aromatic heterocyclic ring, each of which may have a
substituent; and R.sup.61 and Q.sup.1, and R.sup.62 and Q.sup.2
each may form a fused ring structure.
[0046] [19] A compound represented by Formula (6):
##STR00022##
[0047] in the formula, R.sup.11, R.sup.12, R.sup.14, and R.sup.15
each independently represent a hydrogen atom, a halogen atom, an
alkyl group, an aryl group, a heterocyclic group, an ethenyl group,
an ethynyl group, an amino group, an acyl group, an alkoxy group,
an aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and at least two of R.sup.11,
R.sup.12, R.sup.14, and R.sup.15 are atoms or groups other than
hydrogen atoms; X.sup.1 and X.sup.2 each independently represent a
halogen atom, an alkyl group, an aryl group, a heterocyclic group,
a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio
group, an arylthio group, an ethenyl group, or an ethynyl group,
each of which may have a substituent, and X.sup.1 and X.sup.2 may
be bonded to each other to form a ring; R.sup.31 to R.sup.35 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, a cyano group, an
alkoxy group, an aryloxy group, an alkylthio group, or an arylthio
group, each of which may have a substituent, and any one of
R.sup.31, R.sup.32, R.sup.33, R.sup.34 or R.sup.35 is a hydrogen
atom; R.sup.51 and R.sup.52 each independently represent an alkyl
group, an aryl group, a heteroaryl group, an amino group, an acyl
group, an alkoxy group, an aryloxy group, an alkylthio group, or an
arylthio group, each of which may have a substituent; Q.sup.1 and
Q.sup.2 each independently represent an aromatic hydrocarbon ring
or an aromatic heterocyclic ring, each of which may have a
substituent; and L.sup.1 and L.sup.2 each independently represent
any one of Formula (L-1), Formula (L-2), Formula (L-3) or Formula
(L-4);
##STR00023##
[0048] in the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent; and A represents --O--, --S--, or --NH--.
[0049] The luminescent particle of the present invention has an
emission maximum wavelength in a long wavelength range of 680 nm or
longer and exhibits a high quantum yield and is useful in various
assays. The compound of the present invention has an emission
maximum wavelength in a long wavelength range of 680 nm or longer
and exhibits a high quantum yield in the particles.
BRIEF DESCRIPTION OF THE DRAWINGS
[0050] FIG. 1 shows a 400 MHz .sup.1H NMR spectrum of Compound
(4).
[0051] FIG. 2 shows a 400 MHz .sup.1H NMR spectrum of Compound
(7).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0052] Hereinafter, embodiments of the present invention will be
described in detail.
[0053] In the present specification, the numerical range indicated
by using "to" means a range including numerical values described
before and after "to" as a minimum value and a maximum value,
respectively.
[0054] It is known that an ordinary dye compound is influenced by
association in the case where the amount of incorporation into
particles is increased, and therefore the quantum yield decreases
(this is also referred to as concentration quenching). In
particular, in the case of being incorporated into particles, a
fluorescent dye compound having a long absorption wavelength of 650
nm or longer tends to exhibit concentration quenching, whereby it
is difficult to maintain a quantum yield.
[0055] Inclusion of a conjugated substituent in the compound of the
present invention makes it possible to emit light of long
wavelength and inclusion of a plurality of substituents in the
dipyrromethene skeleton makes it also possible to suppress a
decrease in quantum yield in the polymer particles. As a factor of
suppressing a decrease in quantum yield, suppression of
intermolecular interaction (for example, TE-7C interaction) by a
plurality of substituents projecting in a direction perpendicular
to the dipyrromethene skeleton is considered. According to the
compound of the present invention, it is possible to produce a
luminescent particle (preferably a fluorescent particle, more
preferably a fluorescent nanoparticle) having high luminance,
particularly in the long wavelength range. In the case where the
luminescent particle of the present invention is a fluorescent
particle, the luminance refers to fluorescence intensity. According
to the present invention, since the luminescence quantum yield is
high in the region of the window of the living body (in the
vicinity of 650 to 900 nm which is a near-infrared wavelength range
which is easy to transmit through the living body), the sensitivity
of sensing using luminescence can be improved.
[0056] [Luminescent Particle of Present Invention]
[0057] The luminescent particle of the present invention is a
luminescent particle containing at least one kind of compound
represented by Formula (1) and a particle.
##STR00024##
[0058] The meaning of each symbol in Formula (I) is as defined in
the present specification.
[0059] In the present specification, the alkyl group may be linear,
branched, cyclic or a combination thereof, and the number of carbon
atoms in the linear or branched alkyl group is preferably 1 to 36,
more preferably 1 to 18, still more preferably 1 to 12, and
particularly preferably 1 to 6. The cyclic alkyl group may be, for
example, a cycloalkyl group having 3 to 8 carbon atoms. Specific
examples of the alkyl group include a methyl group, an ethyl group,
an n-propyl group, an isopropyl group, an n-butyl group, an
iso-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl
group, an n-hexyl group, an n-heptyl group, an n-octyl group, an
n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl
group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl
group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl
group, and a cyclohexyl group.
[0060] In the present specification, the aryl group is preferably
an aryl group having 6 to 48 carbon atoms, more preferably an aryl
group having 6 to 24 carbon atoms, and still more preferably an
aryl group having 6 to 14 carbon atoms, examples thereof include a
phenyl group, a naphthyl group, an anthryl group, a pyrenyl group,
a phenanthrenyl group, a biphenyl group, and a fluorenyl group.
[0061] In the present specification, the heterocyclic group is
preferably any of 5- to 7-membered substituted or unsubstituted,
saturated or unsaturated, aromatic or non-aromatic, monocyclic or
fused heterocyclic groups. The heterocyclic group is preferably a
heterocyclic group having a ring-constituting atom selected from a
carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom and
having at least one hetero atom selected from a nitrogen atom, an
oxygen atom and a sulfur atom, and more preferably a 5- or
6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.
Examples of the heterocyclic group include a furyl group, a
benzofuryl group, a dibenzofuryl group, a thienyl group, a
benzothienyl group, a dibenzothienyl group, a pyridyl group, a
pyrimidinyl group, a quinolyl group, an isoquinolyl group, an
acridinyl group, a phenanthridinyl group, a pteridinyl group, a
pyrazinyl group, a quinoxalinyl group, a pyrimidinyl group, a
quinazolyl group, a pyridazinyl group, a cinnolinyl group, a
phthalazinyl group, a triazinyl group, an oxazolyl group, a
benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, an
imidazolyl group, a benzimidazolyl group, a pyrazolyl group, an
indazolyl group, an isoxazolyl group, a benzisoxazolyl group, an
isothiazolyl group, a benzisothiazolyl group, an oxadiazolyl group,
a thiadiazolyl group, a triazolyl group, a tetrazolyl group, a
furyl group, a thienyl group, a pyrrolyl group, an indolyl group,
an imidazopyridinyl group, and a carbazolyl group.
[0062] In the present specification, the acyl group is preferably a
linear or branched alkanoyl group having 2 to 15 carbon atoms, and
examples thereof include an acetyl group, a propionyl group, a
butyryl group, an isobutyryl group, a valeryl group, an isovaleryl
group, a pivaloyl group, a hexanoyl group, a heptanoyl group, and a
benzoyl group.
[0063] In the present specification, the alkoxy group is preferably
an alkoxy group having 1 to 20 carbon atoms, and examples thereof
include a methoxy group, an ethoxy group, a propoxy group, an
n-butoxy group, a pentyloxy group, a hexyloxy group, and a
heptyloxy group.
[0064] In the present specification, the aryloxy group is
preferably an aryloxy group having 6 to 14 carbon atoms, and
examples thereof include a phenoxy group, a naphthoxy group, and an
anthryloxy group.
[0065] The alkylthio group is preferably an alkylthio group having
1 to 30 carbon atoms, and examples thereof include a methylthio
group, an ethylthio group, and an n-hexadecylthio group.
[0066] The arylthio group is preferably an arylthio group having 6
to 30 carbon atoms, and examples thereof include a phenylthio
group, a p-chlorophenylthio group, and an m-methoxyphenylthio
group.
[0067] In the present specification, examples of the halogen atom
include a fluorine atom, a chlorine atom, a bromine atom, and an
iodine atom.
[0068] In the present specification, examples of the aromatic ring
include aromatic hydrocarbon rings such as a benzene ring, a
naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene
ring, a perylene ring, and a terylene ring; aromatic heterocyclic
rings such as an indene ring, an azulene ring, a pyridine ring, a
pyrazine ring, a pyrimidine ring, a pyrazole ring, a pyrazolidine
ring, a thiazolidine ring, an oxazolidine ring, a pyran ring, a
chromene ring, a pyrrole ring, a pyrrolidine ring, a benzimidazole
ring, an imidazoline ring, an imidazolidine ring, an imidazole
ring, a pyrazole ring, a triazole ring, a triazine ring, a diazole
ring, an indoline ring, a thiophene ring, a thienothiophene ring, a
furan ring, an oxazole ring, an oxadiazole ring, a thiazine ring, a
thiazole ring, an indole ring, a benzothiazole ring, a
benzothiadiazole ring, a naphthothiazole ring, a benzoxazole ring,
a naphthoxazole ring, an indolenine ring, a benzindolenine ring, a
pyrazine ring, a quinoline ring, and a quinazoline ring; and fused
aromatic rings such as a fluorene ring and a carbazole ring; among
which aromatic rings having 5 to 16 carbon atoms (aromatic rings
and fused rings containing aromatic rings) are preferable.
[0069] In addition, the aromatic ring may have a substituent, and
the term "aromatic ring" means both an aromatic ring having a
substituent and an aromatic ring having no substituent. As the
substituent of the aromatic ring, the substituents described in
Substituent group A to be mentioned later can be mentioned.
[0070] In the present specification, examples of the amino group
include an amino group; an alkyl-substituted amino group such as a
mono- or dimethylamino group, a mono- or diethylamino group, or a
mono or di(n-propyl)amino group; an amino group substituted with an
aromatic residue such as a mono- or diphenylamino group or a mono-
or a dinaphthylamino group; an amino group substituted with one
alkyl group and one aromatic residue, such as a
monoalkylmonophenylamino group; a benzylamino group, an acetylamino
group, and a phenylacetylamino group. Here, the aromatic residue
means a group in which one hydrogen atom has been removed from an
aromatic ring, and the aromatic ring is as described
hereinabove.
[0071] The alkyl group, aryl group, heterocyclic group, ethenyl
group, ethynyl group, amino group, acyl group, alkoxy group,
aryloxy group, alkylthio group, or arylthio group represented by
R.sup.11 to R.sup.15 may have a substituent. Examples of the
substituent include the substituents described in Substituent group
A below.
[0072] Substituent group A:
[0073] a sulfamoyl group, a cyano group, an isocyano group, a
thiocyanato group, an isothiocyanato group, a nitro group, a
nitrosyl group, a halogen atom, a hydroxy group, an amino group, a
mercapto group, an amido group, an alkoxy group, an aryloxy group,
an alkylthio group, an arylthio group, a carbamoyl group, an acyl
group, an aldehyde group, a carbonyl group, an aryl group, an alkyl
group, an alkyl group substituted with a halogen atom, an ethenyl
group, an ethynyl group, a silyl group, and a trialkylsilyl group
(such as a trimethylsilyl group).
[0074] The alkyl group, aryl group, heterocyclic group, hydroxy
group, alkoxy group, aryloxy group, alkylthio group, arylthio
group, ethenyl group, or ethynyl group represented by X.sup.1 and
X.sup.2 may have a substituent. Examples of the substituent include
the substituents described in Substituent group A.
[0075] The aryl group or heterocyclic group represented by Ar.sup.1
and Ar.sup.2 may have a substituent. Examples of the substituent
include the substituents described in Substituent group A.
[0076] The alkyl group, aryl group, heterocyclic group, ethenyl
group, ethynyl group, amino group, acyl group, alkoxy group,
aryloxy group, alkylthio group, or arylthio group represented by
R.sup.111 to R.sup.116 may have a substituent. Examples of the
substituent include the substituents described in Substituent group
A.
[0077] <Compound Represented by Formula (1)>
[0078] In Formula (1), R.sup.11 to R.sup.15 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent. At least three of R.sup.11 to R.sup.15 represent atoms
or groups other than hydrogen atoms, preferably at least four of
R.sup.11 to R.sup.15 represent atoms or groups other than hydrogen
atoms, and more preferably all of R.sup.11 to R.sup.15 represent
atoms or groups other than hydrogen atoms.
[0079] R.sup.11 and R.sup.15 may be the same or different atoms or
groups, but are preferably the same atoms or groups. R.sup.12 and
R.sup.14 may be the same or different atoms or groups, but are
preferably the same atoms or groups.
[0080] R.sup.11 and R.sup.15 preferably represent a hydrogen atom,
a halogen atom, an alkyl group, an aryl group, a heterocyclic
group, an ethenyl group, or an ethynyl group, more preferably an
aryl group, a heterocyclic group, an ethenyl group, or an ethynyl
group, still more preferably an aryl group or an ethynyl group, and
particularly preferably an aryl group, each of which may have a
substituent.
[0081] R.sup.12 and R.sup.14 preferably represent an alkyl group,
which may have a substituent.
[0082] R.sup.13 preferably represents an aryl group, which may have
a substituent.
[0083] In Formula (1), X.sup.1 and X.sup.2 each independently
represent a halogen atom, an alkyl group, an aryl group, a
heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy
group, an alkylthio group, an arylthio group, an ethenyl group, or
an ethynyl group, each of which may have a substituent, and X.sup.1
and X.sup.2 may be bonded to each other to form a ring.
[0084] X.sup.1 and X.sup.2 preferably represent a halogen atom or
an alkoxy group and more preferably a halogen atom. X.sup.1 and
X.sup.2 are still more preferably a fluorine atom, a methoxy group,
an ethoxy group, an isopropyloxy group, or a t-butyloxy group, each
of which is also preferably substituted with a fluorine atom or an
alkoxy group.
[0085] In Formula (1), Ar.sup.1 and Ar.sup.2 each independently
represent an aryl group or a heterocyclic group, each of which may
have a substituent.
[0086] In Formula (1), L.sup.1 and L.sup.2 each independently
represent any one of Formula (L -1), Formula (L-2), Formula (L-3)
or Formula (L-4).
##STR00025##
[0087] In the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent. A represents --O--, --S--, or --NH--.
[0088] L.sup.1 and L.sup.2 preferably represent any one of Formula
(L-1) or Formula (L-2) and more preferably Formula (L-1).
[0089] R.sup.111 to R.sup.116 are preferably hydrogen atoms.
[0090] <As to Compound Represented by Formula (2)>
[0091] A preferred example of the compound represented by Formula
(1) is a compound represented by Formula (2).
##STR00026##
[0092] In the formula, R.sup.11 to R.sup.15, X.sup.1, X.sup.2,
Ar.sup.1, and Ar.sup.2 are as defined in Formula (1), and the
preferred ranges thereof are also the same as the preferred ranges
in Formula (1). L.sup.21 and L.sup.22 each independently represent
a group represented by Formula (L-1) or Formula (L-2). L.sup.21 and
L.sup.22 preferably represent Formula (L-1).
##STR00027##
[0093] <As to Compound Represented by Formula (3)>
[0094] A preferred example of the compound represented by Formula
(1) is a compound represented by Formula (3).
##STR00028##
[0095] In Formula (3), R.sup.11, R.sup.12, R.sup.14, R.sup.15,
X.sup.1, X.sup.2, A.sup.r1, A.sup.r2, L.sup.1 , and L.sup.2 are as
defined in Formula (1), and preferred ranges thereof are also the
same as the preferred ranges in Formula (1). Provided that at least
two of R.sup.11, R.sup.12, R.sup.14 and R.sup.15 are atoms or
groups other than hydrogen atoms, preferably at least three of
R.sup.11, R.sup.12, R.sup.14 and R.sup.15 are atoms or groups other
than hydrogen atoms, and more preferably R.sup.11, R.sup.12,
R.sup.14 and R.sup.15 are atoms or groups other than hydrogen
atoms.
[0096] In Formula (3), R.sup.31 to R.sup.35 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, a cyano group, an acyl group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent (examples of the substituent include
the substituents described in Substituent group A), and any one of
R.sup.31, R.sup.32, R.sup.34 or R.sup.35 is a group consisting of
two or more atoms. The group consisting of two or more atoms is
preferably an alkyl group, an aryl group, an ethenyl group, an
ethynyl group, an amino group, a cyano group, or an alkoxy group
and more preferably an alkyl group. Among the alkyl groups, an
alkyl group consisting only of carbon atoms and hydrogen atoms or
an alkyl group substituted with a halogen atom is preferable; and
an alkyl group having 1 to 6 carbon atoms and consisting only of
carbon atoms and hydrogen atoms or an alkyl group substituted with
a fluorine atom is more preferable; a methyl group, an isopropyl
group, a t-butyl group, or a trifluoromethyl group is still more
preferable; and a methyl group is particularly preferable.
[0097] <As to Compound Represented by Formula (4)>
[0098] A preferred example of the compound represented by Formula
(1) is a compound represented by Formula (4).
##STR00029##
[0099] In Formula (4), R.sup.12, R.sup.13, R.sup.14, X.sup.1,
X.sup.2, Ar.sup.1, Ar.sup.2, L.sup.1 and L.sup.2 are as defined in
Formula (1), and the preferred ranges thereof are also the same as
the preferred ranges in Formula (1). Provided that at least one of
R.sup.12, R.sup.13 or R.sup.14 is an atom or group other than a
hydrogen atom, preferably at least two of R.sup.12, R.sup.13 and
R.sup.14 are atoms or groups other than hydrogen atoms, and more
preferably R.sup.12, R.sup.13, and R.sup.14 are atoms or groups
other than hydrogen atoms.
[0100] In Formula (4), R.sup.41 and R.sup.42 each independently
represent an aryl group, a heterocyclic group, an ethenyl group, or
an ethynyl group, each of which may have a substituent. Examples of
the substituent include the substituents described in Substituent
group A. R.sup.41 and R.sup.42 are each independently preferably an
aryl group, an ethenyl group, or an ethynyl group, and from the
viewpoint of improving a quantum yield, an aryl group is
preferable, and from the viewpoint of increasing a wavelength, an
ethenyl group or an ethynyl group is preferable. In the case of
being an aryl group, it is preferred to have at least one
substituent at the ortho or meta position of the aryl group, and it
is more preferred to have at least one substituent at the ortho
position of the aryl group. The number of the substituent for the
aryl group is preferably 1 to 3 and more preferably 2 or 3. The
substituent for the aryl group is preferably an alkyl group, more
preferably a methyl group, an isopropyl group, or a t-butyl group,
and still more preferably a methyl group.
[0101] <As to Compound Represented by Formula (7)>
[0102] A preferred example of the compound represented by Formula
(4) is a compound represented by Formula (7).
##STR00030##
[0103] In Formula (7), R.sup.12, R.sup.13, R.sup.14, R.sup.41,
R.sup.42, X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2 are as defined in
Formula (4), and the preferred ranges thereof are also the same as
the preferred ranges in Formula (4). Provided that at least one of
R.sup.12, R.sup.13 or R.sup.14 is an atom or group other than a
hydrogen atom, preferably at least two of R.sup.12, R.sup.13 and
R.sup.14 are atoms or groups other than hydrogen atoms, and more
preferably R.sup.12, R.sup.13, and R.sup.14 are atoms or groups
other than hydrogen atoms. L.sup.23 and L.sup.24 are as defined in
L.sup.21 and L.sup.22, and preferred ranges thereof are also the
same as in L.sup.21 and L.sup.22.
[0104] <As to Compound Represented by Formula (8)>
[0105] A preferred example of the compound represented by Formula
(7) is a compound represented by Formula (8).
##STR00031##
[0106] In Formula (8), R.sup.12, R.sup.14, R.sup.41, R.sup.42,
X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2, L.sup.23, and L.sup.24 are as
defined in Formula (7), and preferred ranges thereof are also the
same as the preferred ranges in Formula (7). Provided that at least
one of R.sup.12 or R.sup.14 is an atom or group other than a
hydrogen atom, and preferably R.sup.12 and R.sup.14 are atoms or
groups other than hydrogen atoms. R.sup.31 to R.sup.35 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, a cyano group, an
alkoxy group, an aryloxy group, an alkylthio group, or an arylthio
group, each of which may have a substituent, and any one of
R.sup.31, R.sup.32, R.sup.33, R.sup.34 or R.sup.35 is a hydrogen
atom. R.sup.31 to R.sup.35 preferably represent a hydrogen atom, a
halogen atom, an alkyl group, an aryl group, an amino group, a
cyano group, an alkoxy group, or an aryloxy group, more preferably
a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an
amino group, or a cyano group, more preferably a hydrogen atom, a
fluorine atom, an alkyl group, or a cyano group, and particularly
preferably a hydrogen atom or a fluorine atom. Most preferably,
R.sup.33 is a hydrogen atom, and R.sup.31, R.sup.32, R.sup.34, and
R.sup.35 are fluorine atoms.
[0107] <As to Compound Represented by Formula (9)>
[0108] A preferred example of the compound represented by Formula
(8) is a compound represented by Formula (9).
##STR00032##
[0109] In Formula (9), R.sup.12, R.sup.14, R.sup.41, R.sup.42,
R.sup.31 to R.sup.35, X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2,
L.sup.23, and L.sup.24 are as defined in Formula (8) and preferred
ranges thereof are also the same as the preferred ranges in Formula
(8). Provided that at least one of R.sup.12 or R.sup.14 is an atom
or group other than a hydrogen atom, and preferably R.sup.12 and
R.sup.14 are atoms or groups other than hydrogen atoms. R.sup.61
and R.sup.62 each independently represent an alkyl group, an
alkenyl group, an aryl group, a heteroaryl group, an amino group,
an acyl group, an alkoxy group, an aryloxy group, an alkylthio
group, or an arylthio group, each of which may have a substituent,
Q' and Q.sup.2 each independently represent an aromatic hydrocarbon
ring or an aromatic heterocyclic ring, each of which may have a
substituent, and R.sup.61 and Q.sup.1, and R.sup.62 and Q.sup.2
each may form a fused ring structure.
[0110] R.sup.61 and R.sup.62 preferably represent an alkyl group,
an aryl group, a heteroaryl group, an amino group, an acyl group,
an alkoxy group, or an aryloxy group, more preferably an alkyl
group, an aryl group, a heteroaryl group, an amino group, an acyl
group, an alkoxy group, or an aryloxy group, still more preferably
an alkyl group, an aryl group, or an alkoxy group, and particularly
preferably an alkyl group. Among the alkyl groups, a methyl group,
an ethyl group, an isopropyl group, or a t-butyl group is
preferable, and a methyl group is particularly preferable.
[0111] Q.sup.1 and Q.sup.2 each independently represent an aromatic
hydrocarbon ring or an aromatic heterocyclic ring, each of which
may have a substituent. Examples of the substituent include the
substituents described in Substituent group A. Q.sup.1 and Q.sup.2
are each preferably an aromatic hydrocarbon ring, more preferably a
benzene ring, a naphthalene ring, an anthracene ring, a
phenanthrene ring, or a pyrene ring, still more preferably a
benzene ring or a naphthalene ring, and particularly preferably a
benzene ring.
[0112] As the group forming a fused ring structure with R.sup.61
and Q.sup.1 and the group forming a fused ring structure with
R.sup.62 and Q.sup.2, a naphthalene ring and an anthracene ring are
preferable.
[0113] As the group containing R.sup.61 and forming Q.sup.1 and the
group containing R.sup.62 and forming Q.sup.1, a tolyl group, a
xylyl group, or a mesityl group is preferable; a xylyl group or a
mesityl group is more preferable; a xylyl group having methyl
groups at both ends of the ortho position relative to the bonding
position with L.sup.23 or L.sup.24, or a mesityl group having
methyl groups at both ends of the ortho position and at the para
position relative to the bonding position with L.sup.23 or L.sup.24
is still more preferable; and a mesityl group having methyl groups
at both ends of the ortho position and at the para position
relative to the bonding position with L.sup.23 or L.sup.24 is
particularly preferable.
[0114] <As to Compound Represented by Formula (5)>
[0115] A preferred example of the compound represented by Formula
(1) is a compound represented by Formula (5).
##STR00033##
[0116] In Formula (5), R.sup.11 to R.sup.15, X.sup.1, X.sup.2,
L.sup.1, and L.sup.2 are as defined in Formula (1), and the
preferred ranges thereof are also the same as the preferred ranges
in Formula (1).
[0117] In Formula (5), R.sup.51 and R.sup.52 each independently
represent an alkyl group, an aryl group, a heteroaryl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent. Examples of the substituent include the substituents
described in Substituent group A. R.sup.51 and R.sup.52 are each
independently preferably an alkyl group, an aryl group, a
heteroaryl group, an amino group, an acyl group, an alkoxy group,
or an aryloxy group, more preferably an alkyl group, an aryl group,
a heteroaryl group, an amino group, an acyl group, an alkoxy group,
or an aryloxy group, and still more preferably an alkyl group or an
alkoxy group. From the viewpoint of improving a quantum yield, it
is preferably an alkyl group, more preferably a methyl group, an
ethyl group, an isopropyl group, or a t-butyl group, and
particularly preferably a methyl group. From the viewpoint of
increasing a wavelength, it is preferably an alkoxy group, more
preferably a methoxy group, an ethoxy group, an isopropyloxy group,
or a t-butyloxy group, and particularly preferably a methoxy
group.
[0118] Q.sup.1 and Q.sup.2 each independently represent an aromatic
hydrocarbon ring or an aromatic heterocyclic ring, each of which
may have a substituent. Examples of the substituent include the
substituents described in Substituent group A. Q .sup.1 and Q.sup.2
are each preferably an aromatic hydrocarbon ring, more preferably a
benzene ring, a naphthalene ring, an anthracene ring, a
phenanthrene ring, or a pyrene ring, still more preferably a
benzene ring or a naphthalene ring, and particularly preferably a
benzene ring. As the group containing R.sup.51 and forming Q.sup.1
and the group containing R.sup.52 and forming Q.sup.1, a tolyl
group, a xylyl group, or a mesityl group is preferable; a xylyl
group or a mesityl group is more preferable; a xylyl group having
methyl groups at both ends of the ortho position relative to the
bonding position with L.sup.1 or L.sup.2, or a mesityl group having
methyl groups at both ends of the ortho position and at the para
position relative to the bonding position with L.sup.1 or L.sup.2
is still more preferable; and a mesityl group having methyl groups
at both ends of the ortho position and at the para position
relative to the bonding position with L.sup.1 or L.sup.2 is
particularly preferable.
[0119] <As to Compound Represented by Formula (6)>
[0120] The compound represented by Formula (5) is more preferably a
compound represented by
[0121] Formula (6).
##STR00034##
[0122] In Formula (6), R.sup.11, R.sup.12, R.sup.14, R.sup.15,
R.sup.51, R.sup.52, X.sup.1, X.sup.2, L.sup.1, L.sup.2, Q.sup.1,
and Q.sup.2 are as defined in Formula (5) and the preferred ranges
thereof are also the same as the preferred ranges in Formula
(5).
[0123] In the formula, R.sup.11, R.sup.12, R.sup.14, and R.sup.15
each independently represent a hydrogen atom, a halogen atom, an
alkyl group, an aryl group, a heterocyclic group, an ethenyl group,
an ethynyl group, an amino group, an acyl group, an alkoxy group,
an aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and at least two of R.sup.11,
R.sup.12, R.sup.14.sub., and R.sup.15 are atoms or groups other
than hydrogen atoms. X.sup.1 and X.sup.2 each independently
represent a halogen atom, an alkyl group, an aryl group, a
heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy
group, an alkylthio group, an arylthio group, an ethenyl group, or
an ethynyl group, each of which may have a substituent, and X.sup.1
and X.sup.2 may be bonded to each other to form a ring. R.sup.31 to
R.sup.35 each independently represent a hydrogen atom, a halogen
atom, an alkyl group, an aryl group, a heterocyclic group, an
ethenyl group, an ethynyl group, an amino group, an acyl group, a
cyano group, an alkoxy group, an aryloxy group, an alkylthio group,
or an arylthio group, each of which may have a substituent, and any
one of R.sup.31, R.sup.32, R.sup.33, R.sup.34 or R.sup.35 is a
hydrogen atom. R.sup.31 to R.sup.35 are as defined in Formula (8),
and the preferred ranges thereof are also the same as the preferred
ranges in Formula (8).
[0124] R.sup.51 and R.sup.52 each independently represent an alkyl
group, an aryl group, a heteroaryl group, an amino group, an acyl
group, an alkoxy group, an aryloxy group, an alkylthio group, or an
arylthio group, each of which may have a substituent. Q.sup.1 and
Q.sup.2 each independently represent an aromatic hydrocarbon ring
or an aromatic heterocyclic ring, each of which may have a
substituent.
[0125] L.sup.1 and L.sup.2 each independently represent any one of
Formula (L-1), (L-2), (L-3) or (L-4).
##STR00035##
[0126] In the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent. A represents --O--, --S--, or --NH--.
[0127] R.sup.11 and R.sup.15 are each independently preferably an
alkyl group, an aryl group, a heterocyclic group, an ethenyl group,
an ethynyl group, or an amino group, more preferably that as
defined in R.sup.41 and R.sup.42, that is, an aryl group, a
heterocyclic group, an ethenyl group, or an ethynyl group, and
still more preferably an aryl group, an ethenyl group, or an
ethynyl group. From the viewpoint of improving a quantum yield, an
aryl group is even more preferable, and from the viewpoint of
increasing a wavelength, an ethenyl group or an ethynyl group is
even more preferable. In the case of being an aryl group, it is
preferred to have at least one substituent at the ortho or meta
position of the aryl group, and it is more preferred to have at
least one substituent at the ortho position. The number of the
substituent for the aryl group is preferably 1 to 3 and more
preferably 2 or 3. The substituent for the aryl group is preferably
an alkyl group, more preferably a methyl group, an isopropyl group,
or a t-butyl group, and still more preferably a methyl group.
[0128] <Specific Examples of Compounds Represented by Formulae
(1) to (9)>
[0129] Specific examples of the compounds represented by Formulae
(1) to (9) are shown below. Me represents a methyl group, Et
represents an ethyl group, and iPr represents an isopropyl
group.
##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040##
##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045##
##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050##
##STR00051## ##STR00052##
[0130] <Amount of Compounds Represented by Formulae (1) to
(6)>
[0131] There is no particular limitation on the content of the
compounds represented by Formulae (I) to (6) for the particles used
in the present invention (that is, the particles before addition of
the compounds represented by Formulae (1) to (6)) as long as the
effect of the invention is not impaired, but it is preferably 0.5
.mu.mol/g to 400 .mu.mol/g, more preferably 1 .mu.mol/g to 300
.mu.mol/g, still more preferably 2 .mu.mol/g to 200 .mu.mol/g, and
particularly preferably 3 .mu.mol/g to 100 .mu.mol/g. There is no
particular limitation on the content of the compounds represented
by Formulae (1) to (6) for the particles used in the present
invention (that is, the particles before addition of the compounds
represented by Formulae (1) to (6)) as long as the effect of the
invention is not impaired, but it is preferably 0.1% by mass to 30%
by mass, more preferably 0.2% by mass to 20% by mass, still more
preferably 0.3% by mass to 10% by mass, and particularly preferably
0.4% by mass to 8% by mass.
[0132] In the luminescent particles of the present invention, at
least one compound represented by Formulae (1) to (6) is used, but
two or more compounds represented by Formulae (1) to (6) may be
used. In the case where two or more compounds represented by
Formulae (1) to (6) are used, it is preferred that the total amount
of the compounds falls within the above range.
[0133] <Method for Producing Compounds Represented by Formulae
(1) to (9)>
[0134] The compounds represented by Formulae (1) to (9) can be
produced, for example, according to a synthesis scheme shown in
Examples which will be described later.
[0135] As an example, the synthesis of Compound (1) is outlined
below. 3-ethyl-2,4-dimethylpyrrole and trifluoroacetic acid are
added to a mixture of 3,5-bis(trifluoromethyl)benzaldehyde and
dichloromethane while cooling with water, followed by stirring at
room temperature, chloranil is added while cooling with water,
followed by stirring at room temperature, and diisopropylethylamine
is added dropwise while cooling with water, followed by stirring at
room temperature. Subsequently, a boron trifluoride-diethyl ether
complex is added dropwise while cooling with water, and the
reaction is carried out by stirring the mixture at room
temperature, whereby Compound (1-A) can be synthesized.
Subsequently, Compound (1-A), 115 mg of
2,4,6-trimethylbenzaldehyde, and dehydrated toluene are mixed and
stirred at room temperature. Piperidine and one piece of
p-toluenesulfonic acid monohydrate are added, and the mixture is
stirred while distilling off the solvent. After allowing to cool,
dehydrated toluene is added and the reaction is carried out by
stirring the mixture while distilling off the solvent, whereby
Compound (1) can be produced.
[0136] As another example, Compound (3) can be produced through
Compound (3-A), Compound (3-B) and Compound (3-C) from
3,5-bis(trifluoromethyl)benzaldehyde and 2,4-dimethylpyrrole as
starting compounds according to the synthesis scheme of
<Synthesis Example 2>in Examples which will be described
later.
[0137] Compound (1) and Compound (3) are within the definition of
the compound represented by Formula (1). The compound represented
by Formula (1) other than Compound (1) and Compound (3) can also be
produced by substituting the compound used in the reaction with a
compound having a substituent corresponding to the desired compound
represented by Formula (.sup.1).
[0138] <Particles>
[0139] The luminescent particles of the present invention include
particles. The material and form of the particles are not
particularly limited, and for example, organic polymer particles
such as polystyrene beads or inorganic particles such as silica gel
and glass beads can be used. Specific examples of the material of
the particles include a homopolymer obtained by polymerizing a
monomer such as styrene, methacrylic acid, glycidyl (meth)acrylate,
butadiene, vinyl chloride, vinyl acetate acrylate, methyl
methacrylate, ethyl methacrylate, phenyl methacrylate, or butyl
methacrylate; a copolymer obtained by polymerizing two or more
monomers; and cellulose and a cellulose derivative. A latex in
which the homopolymer or copolymer is uniformly suspended may also
be used. Examples of the particles include other organic polymer
powders, inorganic substance powders, microorganisms, blood cells,
cell membrane fragments, liposomes, and microcapsules. Latex
particles are preferred as particles.
[0140] In the case where latex particles are used, specific
examples of the material of the latex include polystyrene, a
styrene-acrylic acid copolymer, a styrene-methacrylic acid
copolymer, a styrene-glycidyl (meth)acrylate copolymer, a
styrene-styrene sulfonate copolymer, a methacrylic acid polymer, an
acrylic acid polymer, an acrylonitrile-butadiene-styrene copolymer,
a vinyl chloride-acrylic acid ester copolymer, and polyvinyl
acetate acrylate. As the latex, a copolymer containing at least
styrene as a monomer is preferable, and a copolymer of styrene and
acrylic acid or methacrylic acid is particularly preferable. The
method of preparing the latex is not particularly limited, and the
latex can be prepared by any polymerization method. However, in the
case where the luminescent particle of the present invention is
used by labeling with an antibody, immobilization of the antibody
becomes difficult in the case where a surfactant is present.
Therefore, for the preparation of a latex, it is preferred to use
emulsifier-free emulsion polymerization, that is, emulsion
polymerization without using an emulsifier such as a surfactant, or
it is preferred that a latex is prepared by emulsion polymerization
using an emulsifier such as a surfactant and then the surfactant is
removed or reduced by purification. The method for removing or
reducing the surfactant is not particularly limited, but a
purification method in which the operation of precipitating the
latex by centrifugation and then removing the supernatant is
repeated is preferable.
[0141] In the case where emulsifier-free emulsion polymerization is
used in the preparation of the latex, the average particle diameter
can be controlled in the range of 80 to 300 nm by changing the
reaction temperature, the monomer composition ratio (for example,
the ratio of styrene and acrylic acid), and the amount of
polymerization initiator.
[0142] In the case where emulsion polymerization using a surfactant
(for example, sodium dodecyl sulfate) is used in the preparation of
the latex, the average particle diameter can be controlled in the
range of 30 to 150 nm by changing the amount of the surfactant, the
reaction temperature, the monomer composition ratio (for example,
the ratio of styrene and acrylic acid), and the amount of the
polymerization initiator.
[0143] <Luminescent Particle>
[0144] By including the compound represented by Formula (1), the
luminescent particle of the present invention has an emission
maximum wavelength in the long wavelength range of 680 nm or longer
and exhibits a high quantum yield.
[0145] The emission maximum wavelength refers to a wavelength at
which the absorbance becomes the largest in the absorption
spectrum.
[0146] The emission maximum wavelength of the luminescent particle
of the present invention is 650 nm or longer, preferably 680 nm or
longer, more preferably 700 nm or longer, and particularly
preferably 720 nm or longer. The upper limit of the emission
maximum wavelength of the luminescent particle of the present
invention is not particularly limited, but it is preferably 900 nm
or less and more preferably 800 nm or less.
[0147] The emission maximum wavelength of the luminescent particle
can be measured using a commercially available fluorescence
spectrophotometer, for example, a fluorescence spectrophotometer
RF-5300 PC (manufactured by Shimadzu Corporation).
[0148] The quantum yield of luminescent particles is the ratio of
the number of photons emitted as fluorescence to the number of
photons absorbed by luminescent particles.
[0149] The quantum yield of the luminescent particles of the
present invention is preferably 0.25 or more, more preferably 0.4
or more, still more preferably 0.5 or more, even more preferably
0.6 or more, and particularly preferably 0.7 or more. The upper
limit of the quantum yield is not particularly limited, but
generally it is 1.0 or less.
[0150] The quantum yield of the luminescent particles of the
present invention can be measured using a commercially available
quantum yield measuring apparatus, for example, an absolute PL
quantum yield measuring apparatus C9920-02 manufactured by
Hamamatsu Photonics K.K.
[0151] (Method of measuring average particle diameter (average
particle size) of luminescent particles)
[0152] The average particle diameter of the luminescent particles
of the present invention varies depending on the material of the
particles, the concentration range for measuring the test
substance, the measuring device, and the like, but it is preferably
in the range of 0.001 to 10 .mu.m (more preferably 0.01 to 1
.mu.m), still more preferably in the range of 30 to 500 nm, even
more preferably in the range of 50 to 300 nm, particularly
preferably in the range of 80 to 200 nm, and most preferably in the
range of 100 to 150 nm. The average particle diameter of the
luminescent particles that can be used in the present invention can
be measured with a commercially available particle size
distribution meter or the like. As a method for measuring the
particle size distribution, it is possible to use a method such as
optical microscopy, confocal laser microscopy, electron microscopy,
atomic force microscopy, static light scattering method, laser
diffraction method, dynamic light scattering method, centrifugal
sedimentation method, electric pulse measurement method,
chromatography method, ultrasonic attenuation method, and the like
are known, and devices corresponding to the respective principles
are commercially available. Among these measurement methods, it is
preferable to measure the average particle diameter of the
luminescent particles using a dynamic light scattering method from
the viewpoint of the particle size range and ease of measurement.
Commercially available measuring apparatuses using dynamic light
scattering include a NANOTRAC UPA (available from Nikkiso Co.,
Ltd.), a dynamic light scattering type particle size distribution
measuring apparatus LB-550 (available from Horiba Seisakusho), a
concentrated system particle size analyzer FPAR-1000 (available
from Otsuka Electronics Co., Ltd.), and the like. In the present
invention, the average particle diameter is obtained as a median
diameter (d=50) measured at 25.degree. C. under the conditions of a
viscosity of 0.8872 CP and a refractive index of water of
1.330.
[0153] <Method for Producing Luminescent Particles>
[0154] The method for producing the luminescent particles of the
present invention is not particularly limited, but the luminescent
particles can be produced by mixing particles with at least one
kind of compound represented by Formula (1). For example, the
luminescent particles of the present invention can be produced by
adding a compound represented by Formula (1) to particles such as
latex particles. More specifically, the luminescent particles of
the present invention can be produced by adding a solution
containing a compound represented by Formula (1) to a dispersion
liquid of particles containing at least one of water or a
water-soluble organic solvent (tetrahydrofuran, methanol, or the
like) and stirring the mixture.
[0155] <Dispersion Liquid>
[0156] According to the present invention, there is provided a
dispersion liquid containing the above-mentioned luminescent
particles of the present invention.
[0157] The dispersion liquid can be produced by dispersing the
luminescent particles of the present invention in a dispersion
medium. Examples of the dispersion medium include water, an organic
solvent, and a mixture of water and an organic solvent. An alcohol
such as methanol, ethanol, or isopropanol, an ether-based solvent
such as tetrahydrofuran, or the like can be used as the organic
solvent.
[0158] The solid content concentration of the luminescent particles
in the dispersion liquid is not particularly limited, but it is
generally 0.1% to 20% by mass, preferably 0.5% to 10% by mass, and
more preferably 1% to 5% by mass.
[0159] <Utilization of Luminescent Particles>
[0160] The luminescent particles of the present invention can be
used in a fluorescence detection method for quantifying a protein,
an enzyme, an inorganic compound, or the like as an example of a
specific fluorescence detection method.
[0161] [Compound of Present Invention]
[0162] The present invention further relates to a compound
represented by Formula (3).
##STR00053##
[0163] In the formula, R.sup.11, R.sup.12, R.sup.14, and R.sup.15
each independently represent a hydrogen atom, a halogen atom, an
alkyl group, an aryl group, a heterocyclic group, an ethenyl group,
an ethynyl group, an amino group, an acyl group, an alkoxy group,
an aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and at least two of R.sup.11,
R.sup.12, R.sup.14, and R.sup.15 are atoms or groups other than
hydrogen atoms. X.sup.1 and X.sup.2 each independently represent a
halogen atom, an alkyl group, an aryl group, a heterocyclic group,
a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio
group, an arylthio group, an ethenyl group, or an ethynyl group,
each of which may have a substituent, and X.sup.1 and X.sup.2 may
be bonded to each other to form a ring. Ar.sup.1 and Ar.sup.2 each
independently represent an aryl group or a heterocyclic group, each
of which may have a substituent. R.sup.31 to R.sup.35 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, a cyano group, an
alkoxy group, an aryloxy group, an alkylthio group, or an arylthio
group, each of which may have a substituent, and any one of
R.sup.31, R.sup.32, R.sup.34 or R.sup.35 is a group consisting of
two or more atoms.
[0164] L' and L.sup.2 each independently represent any one of
Formula (L-1), Formula (L-2), Formula (L-3) or Formula (L-4).
##STR00054##
[0165] In the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent. A represents --O--, --S--, or --NH--.
[0166] The preferred range of each substituent in Formula (3) is as
described in the present specification.
[0167] The present invention further relates to a compound
represented by Formula (4).
##STR00055##
[0168] In the formula, R.sup.12, R.sup.13, and R.sup.14 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and at least one of R.sup.12,
R.sup.13 or R.sup.14 is an atom or group other than a hydrogen
atom. X.sup.1 and X.sup.2 each independently represent a halogen
atom, an alkyl group, an aryl group, a heterocyclic group, a
hydroxy group, an alkoxy group, an aryloxy group, an alkylthio
group, an arylthio group, an ethenyl group, or an ethynyl group,
each of which may have a substituent, and X.sup.1 and X.sup.2 may
be bonded to each other to form a ring. Ar.sup.1 and Ar.sup.2 each
independently represent an aryl group or a heterocyclic group, each
of which may have a substituent. R.sup.41 and R.sup.42 each
independently represent an aryl group, a heterocyclic group, an
ethenyl group, or an ethynyl group, each of which may have a
substituent. L.sup.1 and L.sup.2 each independently represent any
one of Formula (L-1), Formula (L-2), Formula (L-3) or Formula
(L-4).
##STR00056##
[0169] In the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent. A represents --O--, --S--, or --NH--. The preferred
range of each substituent in Formula (4) is as described in the
present specification.
[0170] The present invention further relates to a compound
represented by Formula (7).
##STR00057##
[0171] In the formula, R.sup.12, R.sup.13, R.sup.14, R.sup.41,
R.sup.42, X.sup.1, X.sup.2, Ar.sup.1, and Ar.sup.2 are as defined
in Formula (4), provided that at least one of R.sup.12, R.sup.13 or
R.sup.14 is an atom or group other than a hydrogen atom. L.sup.23
and L.sup.24 each independently represent a group represented by
Formula (L-1) or (L-2).
##STR00058##
The preferred range of each substituent in Formula (7) is as
described in the present specification.
[0172] The present invention further relates to a compound
represented by Formula (8).
##STR00059##
[0173] In the formula, R.sup.12, R.sup.14, R.sup.41, R.sup.42,
X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2, L.sup.23, and L.sup.24 are as
defined in Formula (7), R.sup.31 to R.sup.35 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, a cyano group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and any one of R.sup.31, R.sup.32,
R.sup.33, R.sup.34 or R.sup.35 is a hydrogen atom.
[0174] The preferred range of each substituent in Formula (8) is as
described in the present specification.
[0175] The present invention further relates to a compound
represented by Formula (9).
##STR00060##
[0176] In the formula, R.sup.12, R.sup.14, R.sup.41, R.sup.42,
R.sup.31 to R.sup.35, X.sup.1, X.sup.2, Ar.sup.1, Ar.sup.2,
L.sup.23, and L.sup.24 are as defined in Formula (8), R.sup.61 and
R.sup.62 each independently represent an alkyl group, an alkenyl
group, an aryl group, a heteroaryl group, an amino group, an acyl
group, an alkoxy group, an aryloxy group, an alkylthio group, or an
arylthio group, each of which may have a substituent, Q.sup.1 and
Q.sup.2 each independently represent an aromatic hydrocarbon ring
or an aromatic heterocyclic ring, each of which may have a
substituent, and R.sup.61 and Q.sup.1, and R.sup.62 and Q.sup.2
each may form a fused ring structure.
[0177] The preferred range of each substituent in Formula (9) is as
described in the present specification.
[0178] The present invention further relates to a compound
represented by Formula (6).
##STR00061##
[0179] In the formula, R.sup.11, R.sup.12, R.sup.14, and R.sup.15
each independently represent a hydrogen atom, a halogen atom, an
alkyl group, an aryl group, a heterocyclic group, an ethenyl group,
an ethynyl group, an amino group, an acyl group, an alkoxy group,
an aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent, and at least two of R.sup.11,
R.sup.12, R.sup.14, and R.sup.15 are atoms or groups other than
hydrogen atoms. X.sup.1 and X.sup.2 each independently represent a
halogen atom, an alkyl group, an aryl group, a heterocyclic group,
a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio
group, an arylthio group, an ethenyl group, or an ethynyl group,
each of which may have a substituent, and X.sup.1 and X.sup.2 may
be bonded to each other to form a ring. R.sup.31 to R.sup.35 each
independently represent a hydrogen atom, a halogen atom, an alkyl
group, an aryl group, a heterocyclic group, an ethenyl group, an
ethynyl group, an amino group, an acyl group, an alkoxy group, an
aryloxy group, an alkylthio group, or an arylthio group, each of
which may have a substituent and any one of R.sup.31, R.sup.32,
R.sup.33, R.sup.34 or R.sup.35 is a hydrogen atom. R.sup.51 and
R.sup.52 each independently represent an alkyl group, an aryl
group, a heteroaryl group, an amino group, an acyl group, an alkoxy
group, an aryloxy group, an alkylthio group, or an arylthio group,
each of which may have a substituent. Q.sup.1 and Q.sup.2 each
independently represent an aromatic hydrocarbon ring or an aromatic
heterocyclic ring, each of which may have a substituent.
[0180] L.sup.1 and L.sup.2 each independently represent any one of
Formula (L-1), (L-2), (L-3) or (L-4).
##STR00062##
[0181] In the formulae, R.sup.111 to R.sup.116 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, an ethenyl group, an ethynyl group, an
amino group, an acyl group, an alkoxy group, an aryloxy group, an
alkylthio group, or an arylthio group, each of which may have a
substituent. A represents --O--, --S--, or --NH--.
[0182] The preferred range of each substituent in Formula (6) is as
described in the present specification.
[0183] The compound represented by Formula (6) can be produced by a
method similar to the method described in the foregoing section
<Method for producing compounds represented by Formulae (1) to
(5)>in the present specification.
[0184] Hereinafter, the present invention will be described in more
detail with reference to the Examples of the present invention. The
materials, amounts of use, proportions, treatment contents,
treatment procedures, and the like shown in the following Examples
can be appropriately modified without departing from the spirit and
scope of the present invention. Therefore, the scope of the present
invention should not be interpreted restrictively by the following
specific examples.
EXAMPLES
[0185] The Terms have the Following Meanings.
[0186] TLC: thin layer chromatography
[0187] MS: mass spectrometry
[0188] ESI: electrospray ionization
[0189] NMR: nuclear magnetic resonance
[0190] rt: room temperature
[0191] Me: methyl
[0192] Et: ethyl
[0193] iPr: isopropyl
[0194] PL: photoluminescence
[0195] TEA: triethylamine
[0196] THF: tetrahydrofuran
[0197] v/v: volume/volume
[0198] The structures of Compounds (1) to (12) and Comparative
Compound (1) are shown below.
##STR00063## ##STR00064## ##STR00065## ##STR00066##
##STR00067##
<Synthesis Example 1> Synthesis of Compound (1)
##STR00068##
[0200] Synthesis of Compound (1-A)
[0201] 1.00 g of 3,5-bis(trifluoromethyl)benzaldehyde and 20 mL of
dichloromethane were introduced into a 100 mL three-neck flask
under a nitrogen atmosphere, followed by stirring at room
temperature. While cooling with water, 0.98 g of
3-ethyl-2,4-dimethylpyrrole was added dropwise, followed by
addition of two drops of trifluoroacetic acid and then stirring at
room temperature for 30 minutes. 1.0 g of chloranil was added while
cooling with water, followed by stirring at room temperature for 10
minutes, and then 3.67 g of diisopropylethylamine (NiPr.sub.2Et)
was added dropwise while cooling with water, followed by stirring
at room temperature for 15 minutes. Subsequently, 5.6 mL of a boron
trifluoride-diethyl ether complex was added dropwise while cooling
with water, followed by stirring at room temperature for 30
minutes. Saturated sodium hydrogencarbonate and toluene were added
dropwise, and the organic layer obtained by extraction and liquid
separation was preliminarily dried over anhydrous sodium sulfate
and then concentrated under reduced pressure. The resulting crude
product was purified by silica gel column chromatography
(developing solvent: hexane/ethyl acetate) and recrystallized from
methanol to obtain 1.28 g of Compound (I-A).
[0202] .sup.1H NMR(CDCl.sub.3, 400MHz): .delta. 8.03(s, 1H),
7.83(s, 2H), 2.54(s, 6H), 2.31(q, J=7.6Hz, 4H), 1.21(s, 6H),
1.00(t, J=7.6Hz, 6H).
[0203] Synthesis of Compound (1)
[0204] 100 mg of Compound (1-A), 115 mg of
2,4,6-trimethylbenzaldehyde and 5 mL of dehydrated toluene were
introduced into a 100 mL three-neck flask, followed by stirring at
room temperature. I mL of piperidine and one piece of
p-toluenesulfonic acid monohydrate (manufactured by Wako Pure
Chemical Industries, Ltd., special grade chemical) were added,
followed by stirring for 1 hour while distilling off the solvent at
140.degree. C. After allowing to cool, 5 mL of dehydrated toluene
was added, followed by stirring for 1 hour while distilling off the
solvent at 140.degree. C. The crude product obtained by
concentrating the reaction liquid under reduced pressure was
purified by preparative TLC (developing solvent: hexane/ethyl
acetate) and recrystallized from methanol to obtain 71 mg of
Compound (1). Identification of the compound was carried out by
.sup.1H-NMR and ESI-MS.
[0205] 1H NMR(CDCl3, 400MHz): .delta. 8.06(s, 1H), 7.87(s, 2H),
7.38(d, J=17.2Hz, 2H), 7.32(d, J=17.2Hz, 2H), 6.93(s, 4H), 2.63(q,
J=7.6Hz, 4H), 2.44(s, 12H), 2.30(s, 6H), 1.27(s, 6H), 1.17(t,
J=7.6Hz, 6H).
[0206] ESI-MS: [M-H].sup.-=775.8
<Synthesis Example 2> Synthesis of Compound (3)
##STR00069##
[0208] Synthesis of Compound (3-A)
[0209] 16.22 g of 3,5-bis(trifluoromethyl)benzaldehyde and 200 mL
of dichloromethane were introduced into a 1 L three-neck flask
under a nitrogen atmosphere, followed by stirring at room
temperature. 15.75 g of 2,4-dimethylpyrrole was added dropwise
while cooling with water, followed by adding five drops of
trifluoroacetic acid and then stirring at room temperature for 30
minutes. 19.45 g of chloranil was added while cooling with water,
followed by stirring at room temperature for 30 minutes, and 80 mL
of diisopropylethylamine (NiPr.sub.2Et) was added dropwise while
cooling with water, followed by stirring at room temperature for 30
minutes. Subsequently, 85 mL of a boron trifluoride-diethyl ether
complex (BF.sub.3.Et.sub.2O) was added dropwise while cooling with
water, followed by stirring at room temperature for 30 minutes. 400
mL of saturated sodium hydrogen carbonate was added dropwise, and
the organic layer obtained by extraction and liquid separation was
preliminarily dried over anhydrous sodium sulfate and then
concentrated under reduced pressure. The resulting crude product
was purified by silica gel column chromatography (developing
solvent: hexane/ethyl acetate) and then recrystallized from ethanol
to obtain 4.40 g of Compound (3-A).
[0210] Synthesis of Compound (3-B)
[0211] 3.05 g of Compound (3-A) and 60 mL of
1,1,1,3,3,3-hexafluoro-2-propanol were introduced into a 300 mL
three-neck flask, followed by stirring at room temperature. 3.60 g
of N-iodosuccinimide was introduced, followed by stirring at room
temperature for 1.5 hours. After concentrating the reaction liquid
under reduced pressure, 50 mL of an aqueous sodium thiosulfate
solution (10 g of sodium thiosulfate dissolved therein) and 100 mL
of methylene chloride were added, and the organic layer obtained by
extraction and liquid separation was preliminarily dried over
anhydrous sodium sulfate and then concentrated under reduced
pressure. The resulting crude product was recrystallized from
ethanol to obtain 3.90 g of Compound (3-B).
[0212] Synthesis of Compound (3-C)
[0213] 2.2 g of Compound (3-B), 2.6 g of
2,4,6-trimethylbenzaldehyde and 40 mL of dehydrated toluene were
introduced into a 100 mL three-neck flask, followed by stirring at
room temperature. 4 mL of piperidine was introduced, followed by
stirring at 65.degree. C. for 1 hour. The crude product obtained by
concentrating the reaction liquid under reduced pressure was
purified by silica gel column chromatography (developing solvent:
hexane/ethyl acetate) and recrystallized from ethanol to obtain 2.4
g of Compound (3-C).
[0214] Synthesis of Compound (3)
[0215] 96 mg of Compound (3-C), 64 mg of
2,4,6-trimethylphenylboronic acid, 130 mg of cesium fluoride, and
10 mL of methoxycyclopentane were introduced into a 100 mL
three-neck flask, followed by degassing under reduced pressure
while stirring at room temperature, and the reaction system was set
to a nitrogen atmosphere. 63 mg of SPhos Pd G3 (manufactured by
Sigma-Aldrich, Inc.) was added thereto, followed by heating under
reflux for 1 hour. 10 mL of a saturated aqueous ammonium chloride
solution and 10 mL of ethyl acetate were added, and the organic
layer obtained by extraction and liquid separation was
preliminarily dried over anhydrous sodium sulfate and then
concentrated under reduced pressure. The resulting crude product
was purified by preparative TLC (developing solvent: hexane/ethyl
acetate) and then recrystallized from ethanol to obtain 16 mg of
Compound (3). Identification of the compound was carried out by
.sup.1H-NMR and ESI-MS.
[0216] 1H NMR(CDCl3, 400MHz): .delta. 8.02(s, 1H), 8.00(s, 2H),
7.42(d, J=22.4Hz, 2H), 6.92(s, 4H), 6.80(s, 4H), 6.67(d, J=22.4Hz,
2H), 2.27(s, 6H), 2.17(s, 6H), 2.16(s, 6H), 2.11(s, 12H), 2.01(s,
12H).
[0217] ESI-MS: [M-H].sup.-=955.8
<Synthesis Example 3> Synthesis of Compound (2)
[0218] The synthesis was carried out in the same manner as in the
synthesis of Compound (3), except that
3,5-bis(trifluoromethyl)benzaldehyde was replaced by
2,3,4,5,6-pentafluorobenzaldehyde and 2,4-dimethylpyrrole was
replaced by 2,4-dimethyl-3-ethylpyrrole. The resulting crude
product was purified by silica gel column chromatography
(developing solvent: hexane/ethyl acetate) and then recrystallized
from dichloromethane/methanol to obtain 8 mg of Compound (2).
Identification of the compound was carried out by .sup.1H-NMR
measurement, thus confirming the same NMR spectrum as in Org.
Biomol. Chem., 2010, Vol. 8, pp. 4546 to 4553.
<Synthesis Example 4> Synthesis of Compound (4)
[0219] Compound (4) was synthesized in the same manner as in the
synthesis of Compound (2), except that 2,4,6-trimethylbenzaldehyde
was replaced by o-tolualdehyde. Identification of the compound was
carried out by .sup.1H-NMR and ESI-MS. 400 MHz .sup.1H-NMR spectrum
is shown in FIG. 1.
[0220] ESI-MS: [M-H].sup.-=673.3
<Synthesis Example 5> Synthesis of Compound (5)
[0221] The synthesis was carried out in the same manner as in the
synthesis of Compound (3), except that
3,5-bis(trifluoromethyl)benzaldehyde was replaced by
2,3,5,6-tetrafluorobenzaldehyde. The resulting crude product was
purified by silica gel column chromatography (developing solvent:
hexane/ethyl acetate) and then recrystallized from methanol to
obtain 16 mg of Compound (5). Identification of the compound was
carried out by .sup.1H-NMR and ESI-MS.
[0222] 1H NMR(CDCl.sub.3, 400MHz): .delta. 7.43(s, 1H), 7.39(s,
1H), 7.29-7.21(m, 1H), 6.94(s, 4H), 6.80(s, 4H), 6.69(s, 1H),
6.65(s, 1H), 2.29(s, 6H), 2.23(s, 6H), 2.08(s, 12H), 2.03(s, 12H),
1.33(s, 6H).
[0223] ESI-MS: [M-H].sup.-=891.4
[0224] Compound (5) was also synthesized by the following synthesis
method.
[0225] <Synthesis of Compound (5)>
##STR00070##
[0226] Synthesis of Compound (5-A)
[0227] 1.16 ml of 2,4-dimethylpyrrole and 140 mL of dichloromethane
were introduced into a 500 mL three-neck flask under a nitrogen
atmosphere, followed by stirring at room temperature. 1.0 g of
2,3,5,6-tetrafluorobenzaldehyde and one drop of trifluoroacetic
acid were added, followed by stirring at room temperature for 15
minutes. 1.38 g of chloranil was added, followed by stirring at
room temperature for 15 minutes, and then 6.8 mL of
diisopropylethylamine (NiPr.sub.2Et) was added dropwise while
cooling with water, followed by stirring at room temperature for 20
minutes. Subsequently, 7.8 mL of a boron trifluoride-diethyl ether
complex (BF.sub.3. Et.sub.2O) was added dropwise while cooling with
water, followed by stirring at room temperature for 30 minutes. 400
mL of saturated sodium hydrogen carbonate was added dropwise, and
the organic layer obtained by dichloromethane extraction and liquid
separation was preliminarily dried over anhydrous sodium sulfate
and then concentrated under reduced pressure. The resulting crude
product was purified by silica gel column chromatography
(developing solvent: hexane/ethyl acetate) and then recrystallized
from methanol to obtain 360 mg of Compound (5-A).
[0228] Synthesis of Compound (5-B)
##STR00071##
[0229] 300 mg of Compound (5-A) and 8 mL of
1,1,1,3,3,3-hexafluoro-2-propanol were introduced into a 300 mL
three-neck flask, followed by stirring at room temperature. 409 mg
of N-iodosuccinimide was introduced, followed by stirring at room
temperature for 1.5 hours. After concentrating the reaction liquid
under reduced pressure, 40 mL of methylene chloride was added, and
the organic layer obtained by extraction and liquid separation was
preliminarily dried over anhydrous sodium sulfate, filtered and
concentrated under reduced pressure. Ethanol was added to the
resulting crude product, followed by dispersion, washing and
filtration to obtain 382 mg of Compound (5-B).
[0230] Synthesis of Compound (5-C)
##STR00072##
[0231] 278 mg of Compound (5-B), 564 mg of
2,4,6-trimethylphenylboronic acid, 653 mg of cesium fluoride, and
43 mL of methoxycyclopentane were introduced into a 100 mL
three-neck flask, followed by degassing under reduced pressure
while stirring at room temperature, and the reaction system was set
to a nitrogen atmosphere. 269 mg of SPhos Pd G3 (manufactured by
Sigma-Aldrich, Inc.) was added thereto, followed by heating under
reflux for 1 hour. 250 mL of ethyl acetate was added, and the
organic layer obtained by extraction and liquid separation was
preliminarily dried over anhydrous sodium sulfate and then
concentrated under reduced pressure. The resulting crude product
was purified by silica gel column chromatography (developing
solvent: hexane/ethyl acetate) and then dissolved in 5 ml of
dichloromethane, 15 ml of methanol was further added, and then
dichloromethane was distilled off, followed by reprecipitation. The
precipitate was filtered to obtain 206 mg of Compound (5-C).
[0232] Synthesis of Compound (5)
##STR00073##
[0233] 50 mg of Compound (5-C), 5 ml of toluene, 46 .mu.l of
2,4,6-trimethylbenzaldehyde, 400 IA of piperidine and one piece of
p-toluenesulfonic acid were introduced into a 100 mL three-neck
flask, followed by heating under reflux under nitrogen for 1 hour.
After further adding 46 .mu.l of 2,4,6-trimethylbenzaldehyde,
followed by heating under reflux for 1 hour, 200 .mu.l of
piperidine was further added, followed by heating under reflux for
another 1 hour. After completion of the reaction, the reaction
liquid was concentrated under reduced pressure. The resulting crude
product was purified by silica gel column chromatography
(developing solvent: hexane/toluene) and then dissolved in 3 ml of
dichloromethane, 15 ml of methanol was added, and then
dichloromethane was distilled off, followed by reprecipitation to
obtain 15 mg of Compound (5). Identification of the compound was
carried out by .sup.1H-NMR and ESI-MS.
<Synthesis Example 6> Synthesis of Compound (6)
##STR00074##
[0235] Synthesis of Compound (6-A)
[0236] 1.00 g of 2,3,5,6-tetrafluorobenzaldehyde and 20 mL of
dichloromethane were introduced into a 100 mL three-neck flask
under a nitrogen atmosphere, followed by stirring at room
temperature. 0.98 g of 3-ethyl-2,4-dimethylpyrrole was added
dropwise while cooling with water, followed by addition of two
drops of trifluoroacetic acid and then stirring at room temperature
for 15 minutes. 1.0 g of chloranil was added while cooling with
water, followed by stirring at room temperature for 10 minutes, and
3.67 g of diisopropylethylamine was added dropwise while cooling
with water, followed by stirring at room temperature for 15
minutes. Subsequently, 5.6 mL of a boron trifluoride-diethyl ether
complex was added dropwise while cooling with water, followed by
stirring at room temperature for 60 minutes. Saturated sodium
hydrogen carbonate and toluene were added dropwise, and the organic
layer obtained by extraction and liquid separation was
preliminarily dried over anhydrous sodium sulfate and then
concentrated under reduced pressure. The resulting crude product
was purified by silica gel column chromatography (developing
solvent: toluene) and recrystallized from methanol to obtain 0.76 g
of Compound (6-A).
[0237] 1H NMR(CDCl3, 400MHz): .delta. 7.20-7.30(m, 1H), 2.54(s,
6H), 2.33(q, J=7.6Hz, 4H), 1.51(s, 6H), 1.01(t, J=7.6Hz, 6H).
[0238] Synthesis of Compound (6)
[0239] 181 mg of Compound (6-A), 237 mg of
2,4,6-trimethylbenzaldehyde and 10 mL of dehydrated toluene were
introduced into a 100 mL three-neck flask, followed by stirring at
room temperature. 2 mL of piperidine and two pieces of
p-toluenesulfonic acid monohydrate (manufactured by Wako Pure
Chemical Industries, Ltd., special grade chemical) were added,
followed by stirring for 1 hour while distilling off the solvent at
140.degree. C. The crude product obtained by concentrating the
reaction liquid under reduced pressure was purified by silica gel
column chromatography (developing solvent: toluene) and then
recrystallized from acetonitrile to obtain 194 mg of Compound (6).
Identification of the compound was carried out by .sup.1H-NMR and
ESI-MS.
[0240] .sup.1H NMR(CDCl3, 400MHz): .delta. 7.40(d, J=17.2Hz, 2H),
7.32(d, J=17.2Hz, 2H), 7.20-7.30(m, 1H), 6.93(s, 4H), 2.66(q,
J=7.6Hz, 4H), 2.44(s, 12H), 2.30(s, 6H), I .55(s, 6H), 1.19(t,
J=7.6Hz, 6H).
[0241] ESI-MS: [M-H].sup.-=711.7
<Synthesis Example 7> Synthesis of Compound (7)
[0242] Compound (7) was synthesized in the same manner as in the
synthesis of Compound (2), except that 2,4,6-trimethylbenzaldehyde
was replaced by 2,4,6-trimethoxybenzaldehyde. Identification of the
compound was carried out by .sup.1H-NMR and ESI-MS. 400
MHz.sup.1H-NMR spectrum is shown in FIG. 2.
[0243] ESI-MS: [M+H].sup.+=825.3
<Synthesis Example 8> Synthesis of Compound (8)
##STR00075##
[0245] Synthesis of Compound (8)
[0246] 97 mg of Compound (3-C), 58 mg of
2-ethynyl-1,3,5-trimethylbenzene, 3.8 mg of copper (I) iodide, 4 mL
of THF, and 1 mL of triethylamine were introduced into a 50 mL
two-neck flask, followed by degassing under reduced pressure while
stirring at room temperature, and the reaction system was set to a
nitrogen atmosphere. Tetrakis(triphenylphosphine)palladium (0)
(Pd(PPh.sub.3).sub.4) was added thereto, followed by heating under
reflux for 2 hours. The solvent was removed by distillation under
reduced pressure, and 30 mL of dichloromethane was added thereto,
followed by washing with 20 mL of water and 20 mL of a saturated
aqueous sodium chloride solution. The organic layer was
preliminarily dried over anhydrous sodium sulfate and concentrated
under reduced pressure. The resulting crude product was purified by
silica gel column chromatography (developing solvent:
hexane/toluene) and then recrystallized from methanol to obtain 26
mg of Compound (8). Identification of the compound was carried out
by .sup.11-1-NMR and ESI-MS.
[0247] .sup.1H NMR(CDCl3, 400MHz): .delta. 8.60(s, 1H), 8.56(s,
1H), 8.09(s, 1H), 7.90(s, 2H), 7.41(s, 1H), 7.37(s, 1H), 6.88(s,
4H), 6.85(s, 4H), 2.36(s, 12H), 2.34(s, 12H), 2.28(s, 6H), 2.27(s,
6H).
[0248] ESI-MS: [M-H].sup.-=1003.5
[0249] Synthesis of Compound (9)
[0250] Compound (9) was synthesized in the same manner as in the
method of synthesizing Compound (5) through Compounds (5-A) to
(5-C), except that 2,4,6-trimethylbenzaldehyde in the synthesis of
Compound (5) was replaced by benzaldehyde.
[0251] Synthesis of Compound (10)
[0252] Compound (10) was synthesized in the same manner as in the
method of synthesizing Compound (5) through Compounds (5-A) to
(5-C), except that 2,3,5,6-tetrafluorobenzaldehyde in the synthesis
of Compound (5) was replaced by 2,4,6-trimethylbenzaldehyde.
[0253] Synthesis of Compound (11)
[0254] Compound (11) was synthesized in the same manner as in the
method of synthesizing Compound (5) through Compounds (5-A) to
(5-C), except that 2,4,6-trimethylbenzaldehyde in the synthesis of
Compound (5) was replaced by 2-formylnaphthalene.
[0255] Synthesis of Compound (12)
[0256] Compound (12) was synthesized in the same manner as in the
method of synthesizing Compound (5) through Compounds (5-A) to
(5-C), except that 2,4,6-trimethylbenzaldehyde in the synthesis of
Compound (5) was replaced by 2,6-dimethoxybenzaldehyde.
[0257] Synthesis of Compound (13)
[0258] Compound (13) was synthesized in the same manner as in the
method of synthesizing Compound (5) through Compounds (5-A) to
(5-C), except that 2,4,6-trimethylbenzaldehyde in the synthesis of
Compound (5) was replaced by 9-anthraldehyde.
[0259] Synthesis of Compound (14)
[0260] Compound (14) was synthesized in the same manner as in the
method of synthesizing Compound (5) through Compounds (5-A) to
(5-C), except that 2,4,6-trimethylbenzaldehyde in the synthesis of
Compound (5) was replaced by 4-(N,N-diphenylamino)benzaldehyde.
[0261] Comparative Compound (1) is Compound 5 of JP3442777B.
[0262] (Preparation of fluorescent latex dispersion liquid)
[0263] Fluorescent latex particles were prepared. As the latex
particles, particles having an average particle diameter of 150 nm
prepared by polymerization in a state that a 9/1 (mass ratio)
mixture of styrene and acrylic acid was dispersed in water were
used. The average particle diameter was measured by a dynamic light
scattering method. THF (5 mL) was added dropwise to the
above-prepared latex dispersion liquid having a solid content of 2%
(25 mL, 500 mg in terms of solids), followed by stirring for 10
minutes. A THF solution (2.5 mL) of the test compound (any one of
Compound (1), Compound (2), Compound (3), Compound (4), Compound
(5), Compound (6), Compound (7), Compound (8), Compound (9),
Compound (10), Compound (11), Compound (12) or Comparative Compound
(1)) was added dropwise thereto over 15 minutes. The amounts of the
compounds used for each sample are summarized in Table 1. The
amount of the compound in Table 1 in terms of .mu.mol/g represents
the number of moles of the compound used relative to 1 g of the
solids in the latex. Completion of the dropwise addition of the
test compound was followed by stirring for 30 minutes and
concentration under reduced pressure to remove THF. Thereafter, the
particles were precipitated by centrifugation, followed by addition
of ultra-pure water, and then dispersed again to produce a
fluorescent latex dispersion liquid having a solid content
concentration of 2%.
[0264] (Evaluation of Fluorescent Latex Dispersion Liquid)
[0265] The emission maximum wavelength and the quantum yield of the
above-prepared fluorescent latex dispersion liquid having a solid
content concentration of 2% by mass were evaluated. A latex
dispersion liquid diluted 200-fold with ultrapure water was used.
Evaluation was carried out using a fluorescence spectrophotometer
RF-5300 PC (manufactured by Shimadzu Corporation) for the
measurement of the emission maximum wavelength and the relative
fluorescence intensity, and using an absolute PL quantum yield
measuring apparatus C9920-02 (manufactured by Hamamatsu Photonics
K.K.) for the measurement of the quantum yield. The results
evaluated according to the following standards are summarized in
Table 1, Table 2, and Table 3. The relative fluorescence intensity
indicates the ratio of the fluorescence intensities at the emission
maximum wavelength.
[0266] The evaluation standards for the emission maximum wavelength
are shown below.
[0267] S: 720 nm or longer
[0268] A: 700 nm or longer and shorter than 720 nm
[0269] B: 680 nm or longer and shorter than 700 nm
[0270] C: 650 nm or longer and shorter than 680 nm
[0271] D: Shorter than 650 nm
[0272] The evaluation standards for the quantum yield are shown
below.
[0273] SS: 0.7 or more
[0274] SA: 0.6 or more and less than 0.7
[0275] S: 0.5 or more and less than 0.6
[0276] A: 0.4 or more and less than 0.5
[0277] B: 0.25 or more and less than 0.4
[0278] C: Less than 0.25
TABLE-US-00001 TABLE 1 Amount of Emission compound maximum Quantum
Compound (.mu.mol/g) wavelength yield Remarks Example 1 Compound
(1) 6 B S Present invention Example 2 Compound (1) 12 B S Present
invention Example 3 Compound (2) 12 A A Present invention Example 4
Compound (3) 12 A A Present invention Example 5 Compound (4) 6 A A
Present invention Example 6 Compound (5) 6 A SS Present invention
Example 7 Compound (5) 12 A SS Present invention Example 8 Compound
(6) 6 A A Present invention Example 9 Compound (6) 12 A A Present
invention Example 10 Compound (7) 6 S B Present invention Example
11 Compound (8) 6 S B Present invention Comparative Comparative 6 B
C Comparative Example 1 Compound (1) Example Comparative
Comparative 12 B C Comparative Example 2 Compound (1) Example
TABLE-US-00002 TABLE 2 Amount of Emission compound maximum Quantum
Compound (.mu.mol/g) wavelength yield Remarks Example 12 Compound
(9) 6 B S Present invention Example 13 Compound (9) 12 B A Present
invention Example 14 Compound (10) 6 C SS Present invention Example
15 Compound (10) 12 C SA Present invention Example 16 Compound (11)
6 S B Present invention Example 17 Compound (11) 12 S B Present
invention Example 18 Compound (12) 6 S B Present invention Example
19 Compound (12) 12 S B Present invention Example 34 Compound (13)
6 S B Present invention Example 35 Compound (13) 12 S B Present
invention Example 36 Compound (14) 6 S B Present invention Example
37 Compound (14) 12 S B Present invention
TABLE-US-00003 TABLE 3 Amount of Emission Relative compound maximum
fluorescence Compound (.mu.mol/g) wavelength intensity Example 20
Compound (5) 12 A - (standard) Example 21 Compound (5) 24 A 2-fold
as compared to Example 20 Example 22 Compound (5) 48 A 4-fold as
compared to Example 20 Example 23 Compound (5) 100 A 6-fold as
compared to Example 20 Example 24 Compound (6) 12 A - (standard)
Example 25 Compound (6) 100 A 1.5-fold as compared to Example 24
Example 26 Compound (9) 12 B - (standard) Example 27 Compound (9)
24 B 1.5-fold as compared to Example 26 Example 28 Compound (9) 48
B 2-fold as compared to Example 26 Example 29 Compound (10) 12 C -
(standard) Example 30 Compound (10) 24 C 2-fold as compared to
Example 29 Example 31 Compound (10) 48 C 4-fold as compared to
Example 29
[0279] Fluorescent latex particles were prepared using particles
having an average particle diameter of 100 nm. As the latex
particles, particles having an average particle diameter of 100 nm
prepared by polymerization in a state where a 9/1 (mass ratio)
mixture of styrene and acrylic acid and sodium dodecyl sulfate were
dispersed in water were used. The average particle diameter was
measured by a dynamic light scattering method. Fluorescent latex
particles were prepared in the same manner as in the method for
preparing fluorescent latex particles used in Examples 1 to 12, for
the above-prepared latex dispersion liquid having a solid content
of 2% (25 mL, 500 mg in terms of solids). The same measurements as
those in Examples 1 to 12 were carried out and the evaluation was
carried out according to the same standards. The results are shown
in Table 4.
TABLE-US-00004 TABLE 4 Amount of Emission compound maximum Quantum
Compound (.mu.mol/g) wavelength yield Example 32 Compound (5) 12 A
SA Example 33 Compound (5) 24 A S
[0280] It was found that Compounds (1) to (12) of the present
invention have an emission maximum wavelength in a long wavelength
range and exhibit a high quantum yield in the particles, as
compared with Comparative Compound (1).
* * * * *